Apparatus for determining comcentration of an element in a sample

ABSTRACT

Disclosed is an apparatus for automatically determining the weight or concentration of a compound or element in a solution. A sensing chamber containing at least one ion sensing electrode is provided with a continuous flow of carrier fluid. The solution is mixed with the carrier fluid and the resultant mixture flows to the sensing chamber. The electrical output of the ion sensing electrode continuously indicates the concentration of a specific ion in the liquid mixture reaching the chamber. After the electrical output of the electrode beings to increase, this output is integrated for a predetermined period of time while the mixture flows through the sensing chamber.

Oct. 9, 1973 D, M. H. PLATT 3,764,506

APPARATUS FOR DETERMINING CONCENTRATION OF AN ELEMENT IN A SAMPLE FiledOct. 26, 1971 4 Sheets-Shout \\FROM BATCH COMPRESSED 2| STORAGE AIRSOURCE 23 v) NC 6 Am CYLINDER H9 1 WEIGH CELL SOLENOID GLASS SOURCE TOATMOS- FURNACE 3% PHERE SOLUTION 55 OUT 33 TO PREAMP p OF FIG.2 35CYCLONE 5| NC DRAIN INVENTOR. 56 David M. H. P/arf UNDISSOLVED SOLlDSOUT ATTORNEY Oct. 9, I973 OF AN ELEMENT IN A SAMPLE 4 Sheets-Sheet 2Filed Oct. 26, 1971 mmkzEm wN wumsOw i A z ww 5 30528 mwkzEm E. 3

INVBNTOR.

BY David M. H. P/aff M 0252mm H39. I I I I I I I I I I I E. $55248 03 En 5 w@ .rz II mm a $23595 II. mm fimziu kww I IIIIIIIIIIIII I I L mm@zmmzmm IIIIIIIII I MI I I mm NM Ow mobnozouwzk a m f; H F m jwumfizjzoz M Z n I 9w; N IIIIIIIIII IIW I I L mm W n 0 E3050 0401 oz w n=2w ATTORNEY Oct. 9, 1%73 D M. H. PLATT APPARATUS FOR DETERMININGCONCENTRATlON OF AN ELEMENT IN A SAMPLE 4 Sheets-Shem .j-

INVENTOIL David M. H. P/arf Pmmwm m ImD E mwnEOI mfiam awhw wmmuoma um mFiled Oct. 26, 1971 ATTORNEY Oct. 1973 D. M. H. PLATT APPARATUS FORDETERMINING CONCENTRATION OF AN ELEMENT IN A SAMPLE Filed Oct. 26, 19714 Sheets-Sheet 4 H METER AND CQNTROL CIRCUIT BASIC SOLUTIONI 84 88 I J IACIDIC 32' 34 /(v} SOLUTION V v I j M 86 v 49 89 x} //f l// j J1"; DCL 44 a I L. x a --83 F/g.4

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2 min ATTORNEY United States Patent Office 3,764,506 Patented Oct. 9,1973 3,764,506 APPARATUS FOR DETERMINING CONCENTRA- TION OF AN ELEMENTIN A SAMPLE David M. H. Platt, Harrodsburg, Ky., assignor to CorningGlass Works, Corning, N.Y.

Continuation-impart of application Ser. No. 29,433, Apr. 17, 1970. Thisapplication Oct. 26, 1971, Ser. No. 192,360

Int. Cl. G01n 27/26 US. Cl. 204-195 R Claims ABSTRACT OF THE DISCLOSUREDisclosed is an apparatus for automatically determining the weight orconcentration of a compound or element in a solution. A sensing chambercontaining at least one ion sensing electrode is provided with acontinuous fiow of carrier fluid. The solution is mixed with the carrierfluid and the resultant mixture flows to the sensing chamber. Theelectrical output of the ion sensing electrode continuously indicatesthe concentration of a specific ion in the liquid mixture reaching thechamber. After the electrical output of the electrode begins toincrease, this output is integrated for a predetermined period of timewhile the mixture fiows through the sensing chamber.

CROSS-REFERENCE TO RELATED APPLICATIONS This application is acontinuation-in-part of application Ser. No. 29,433 filed Apr. 17, 1970and now abancloned.

BACKGROUND OF THE INVENTION This invention relates to an apparatus forautomatically determining the weight or concentration of a compound orelement in a mixture of granular solids.

Although the preferred embodiment of this invention relates to thedetermination of the concentration of specific compounds or elementspresent in a batch of raw materials that is to be fed to a glass furnaceor tank, it is also useful for analyzing other granular mixtures such ascement batch, refractory batch, smelter burden, digester feed and thelike, and for analyzing solution.

Raw materials from silos, bins and other containers are combined andmixed prior to being fed to a glass furnace. Evaluations of batch houseoperations have been made in order to improve batch homogeneity, tomaintain batch compositions and to optimize designs for new batchplants. The evaluation and optimization of batch systems is not aguarantee that batch of the proper composition will be delivered to thetank at all times. Problems such as sand in a soda ash silo or defectivescales can still occur and often are not noticed until the tank has beenfilled with off-composition glass. It is therefore desirable to quicklyand reliably analyze batch composition so that batch composition can beaccurately controlled and off-composition glass can be prevented.

Heretofore, the analysis of granular solid material for content ofspecific compounds has been done by traditional wet chemical methodswhich are time consuming and require trained manpower. Moreover, samplesusually must be carried to a central lab for testing. There is thereforea need for an automatically controlled apparatus operable with unskilledlabor which will provide an acceptably accurate analysis of a sample ofglass batch or other granular mixture for such uses as process analysis,error detection and computer controlled processes.

SUMMARY OF THE INVENTION It is therefore an object of the presentinvention to provide an apparatus for quickly and accurately determiningthe weight or concentration of a compound or element in a mixture ofgranular solids or in a solution.

Another object of this invention is to provide an apparatus forcontinuously monitoring the composition of raw materials.

Briefly, the apparatus of this invention comprises means for retaining asample of a solution containing an element, the concentration of whichis to be determined. A chamber containing at least one ion sensingelectrode is connected to means for supplying a stream of carrier fluid.Means are provided for mixing the solution with the carrier fluid sothat the resultant mixture is conveyed to the chamber, the electricaloutput of the ion sensing electrode continuously indicating theconcentration of a specific ion in the liquid mixture reaching thechamber.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a schematic diagram of anapparatus constructed in accordance with the present invention.

FIG. 2 is a schematic circuit diagram in block diagram form of anelectronic circuit for processing electrical signals generated bycomponents in FIG. 1.

FIG. 3 is a chart indicating the components actuated during each step inthe process performed by the apparatus of the present invention.

FIG. 4 is a modification of a portion of the apparatus of FIG. 1 whichpermits the use of an acidic solution for dissolving the sample ofgranular material.

FIG. 5 is a graph illustrating an X-Y recorder plot of the electricaloutput of an ion sensing electrode in response to a pulse of solutionsupplied to the sensing chamber.

FIG. 6 is a modification of a portion of the apparatus of FIG. 1 whichpermits the injection of a solution into a stream of carrier fluid.

DETAILED DESCRIPTION This inventionwill be described in connection witha batch supplying and monitoring system for a glass manufacturingoperation. It is to be understood that this invention is equallyapplicable to the analysis of solutions and other types of rawmaterials. Referring to FIG. 1, batch material flows from a pipe 11 andfalls into a hopper 12 which is connected by a pipe 13 to a glassfurnace or other utilization or storage device. A movable hopper 14 isconnected by way of a movable joint to a pipe 16 which empties into aweigh hopper 18. The position of the movable hopper 14 is controlled byan air cylinder 19 which is connected thereto by an arm 20. A compressedair source 21 is connected by valves 22 and 23 to opposite ends of theair cylinder. Note that the numerals 22 and 23, as well as othernumerals in FIG. 1 which designate valves, have the letters NC or NOlocated adjacent thereto. The letters NC indicate that that valve isnormally closed, and the letters NO indicate that the valve is normallyopen. Thus, the valves 22 and 23 remain closed until they are opened byan electrical signal from a process timer to be hereinafter described.For the sake of simplicity and clarity, no process timer has been shownin the drawings and no lead lines are connected to the valves, all ofwhich are electrically actuated. When the valve 23 is opened the arm 20is forced from the air cylinder, thus moving hopper 14 into the batchintercepting position shown in FIG. 1. The arm 20 is retracted into theair cylinder when the valve 22 is opened, thereby pulling hopper 14 awayfrom the batch emanating orifice of pipe 11. When hopper 14 is in thislatter described position, batch emanating from pipe 11 is interceptedby hopper 12 and delivered to the glass furnace.

When hopper 14 is retracted away from pipe 11, the batch that had beenintercepted thereby empties through pipe 16 'into weigh hopper 18 Whichis suspended from weigh cell 30' by support members 27. At this time acone 24 which is connected by the shaft 26 to a solenoid 28 ismaintained in the position shown by the spring bias of the solenoid. Thebatch received by the weigh hopper 18 is retained therein by cone 24 andthe electrical output 29 of weigh cell 30' is indicative of the weightof the batch. The batch from hopper 18 is dumped into a funnel 31 whenthe solenoid 28 is energized. The batch received by the funnel 31 passesthrough valve 32 into dissolving means such as a tank 3 3, the valve '32being open when the weigh hopper is dumped. In the preferred embodimenthoppers 14 and 18, pipe 16, solenoid 28, cone 24, funnel 31 and valve 32function as means for supplying a sample of granular solids to tank 3-3.This function could be slightly modified by manually supplying a sampleto weight hopper 18 or by manually weighing a sample and supplying itdirectly to tank 33.

The tank 33 is normally vented to the atmosphere by a valve 34-, and thecontents of the tank can be drained through valve 35.

Means must be provided for supplying a solvent to tank 33 to dissolvethe granular material which has been dumped therein. Depending upon thematerial to be dissolved, the solvent may be water, an organic compound,acidic or basic solutions or the like. In the embodiment shown in FIG. 1the solvent is water supplied by a source 38 and a constant flow pump42. This water flows through a valve 39 and nozzle 40' to dislodge anymaterial adhering to the walls of funnel 31. A pump 41 recirculates andstirs the contents of tank 33 to form a solution containing thoseelements the concentrations of which are to be determined. Otherstirring means may be employed such as a paddle wheel located in tank33. A carrier fluid must be provided for mixing with the solution intank 33 and for conveying the resultant mixture of solution and carrierfluid to a sensing chamber 53. To provide this function, water flowsfrom pump 42 through pipe 43, valve 44 and 46 are actuated, the waterflows from the valve 44 through the pipe 49, tank 33, pipe 50 and valve46 to the pipe 48, and the carrier fluid is therefore diverted throughtank 33. Pipe 48 is connected to cyclone 51 where undissolved solids areremoved from the solution and exit from drain 56, the solutioncontinuing through pipe 52 to sensing chamber 53 which contains ionsensing and reference electrodes. Sensing chamber 53 may be of the typedisclosed in application Ser. No. 29,467 entitled Flow-Through Chamberfor Analysis of Continuously Flowing Sample Solution, filed Apr. 17,1970. The solution flows from the sensing chamber through pipe 54 to adrain. No lead has been shown for connecting the reference electrodepotential from the sensing chamber to the electrical circuitryassociated with this invention since such a connection may be made in aconventional manner. The reference electrode could also be connected toa voltage feedback circuit as disclosed in US. Pat. No. 3,649,504entitled System for Controlling the Electrical Field in a FluidAnalyzing Chamber.

FIG. 2 is a schematic circuit diagram of an electronic circuit which maybe used to process the electrical signals developed by portions of theapparatus shown in FIG. 1. The overall function of this circuit is toprocess the electrical signals provided by the weigh cell 38 and an ionsensing electrode in chamber 53 in such a manner that a resultantelectrical signal is produced which is proportional to the concentrationof a specific element detected by the ion sensing electrode divided bythe weight of the sample. The circuit then integrates this resultantelectrical signal fora given time to provide an output indicative of thepercentage of a given type of soluble ions present in the granularmaterial being analyzed. Switches 60-63 are controlled by a processtimer which also controls all of the valves shown in FIG. 1. Valves 22,23, 32, 34, 35, '39, 44 and 46 and solenoid 28 of FIG. 1 areelectrically controlled by switches h Process timer. The

voltage appearing on one of the ion sensing electrodes in sensingchamber 53 is connected by a line to an electrometer 66 which mayinclude a preamplifier 67, subtracter circuit 68, antilog converter 69and an analog-todigital converter 70. The electrical output of the Weighcell of FIG. 1 is connected by a line 29, capacitor 71, high inputimpedance amplifier 72, non-linear transconductor 73 and switch 61 tothe subtracter circuit 68.

The circuit including capacitor 71, amplifier 72 and switch 60, which issometimes referred to as a sample and hold circuit, is required forautomatically referencing the weighing system to zero since the weightof the empty weigh hopper 18 plus the solenoid 28 represents a nonzerocondition. When the weigh hopper '18 is filled with sample material, thecontact is closed, shorting the input of the amplifier 72 to ground andestablishing a zero condition. The contact 60 is then opened and theweigh hopper is dumped so that the voltage coupled to the input of theamplifier 72 represents the weight of the sample which has just beendumped into funnel 31. The output of the non-linear transconductor 73 isthe logarithm of the voltage appearing at the input of the amplifier 72.

The digital output of the analog-to-digital converter is coupled to aprinter-controller 75, the output of which is connected to printer 76. Apulse generator 78 is connected by switch 62 to the printer-controller,and a DC potential source 79 is connected through capacitor 80 andswitch 63 to the printer-controller.

The operation of FIGS. 1 and 2 will now be discussed, reference beingmade to the process timer diagram shown in FIG. 3. This description willrelate to the analysis of glass batch for soluble sodium since sodiumoxide is an important constituent in many glasses and sodium specificion electrodes are readily available. It will be obvious that thedescribed apparatus can be extended or modified to detect any componentfor which there is a specific ion electrode and which can be readilydissolved. The pump 42 maintains a constant flow of Water through theapparatus including cyclone 51 and sensing chamber 53, the dissolvingtank 33 being bypassed since valves 44 and 46 are in the positions shownin FIG. 1. A 5 g.p.m. flow of Water has been found to be satisfactory.The process timer (not shown) is actuated by pushing a start button.Valve 23 is actuated for two seconds, causing movable hopper 14 tointercept a sample of batch emanating from pipe 11. In one embodimentabout g. of glass batch was intercepted by hopper 14. Valve 22 is thenopened for ten seconds and hopper 14 is retracted away from pipe 11, thecontents thereof being dumped into weigh hopper 18. During the fourthstep, the tank inlet valve 32 is opened and the switch 60' is closed,thereby shorting tare capacitor 71 to ground. During the fifth step,valve 32 remains opened, weigh hopper solenoid 28 is actuated, dumpingthe contents of hopper 18 into funnel 31, valve 39 is opened, and waterfrom nozzle 40 flushes the sample from the funnel 31 into tank 3-3. Thedissolving tank may be lined with silicone rubber and may have acapacity of approximately two liters. Step 5 continues for thirtyseconds so that a sufiicient amount of water is delivered to the tank todissolve the sample. Since the flow from nozzle 40 is substantiallyconstant, the amount of water delivered to tank 33 can be regulated bythe period of time during which valve 39 remains open. About 1.5 litersof water was delivered to the tank in thirty seconds, an amount whichcaused the level of the resultant solution to raise to near the top ofthe tank. During step 6, after solenoid 28 has become deenergized andvalve 39 has closed, tank inlet valve 32 remains open for ten secondswhile water from funnel 31 drains into tank 33. During step 7, whichlasts two minutes, the vent valve 34 is closed and switch 61 of FIG. 2is closed. During this step, the recirculation action of pump 41 helpsto dissolve the sample. During the eighth step, four of the contacts ofthe process timer are simultaneously closed for two minutes.

The diverter valves 44 and 46 are switched so that water from pump 42 isdiverted through tank 33. The vent valve 44 and the switch 61 remainclosed during this step. Switch 62 is also closed during step 8. Thevoltage on line 55, which is developed by a sodium ion sensing electrodein sensing chamber 53 is proportional to the logarithm of the sodium ionconcentration. As stated previously, the output from non-lineartransconductor 73 is the logarithm of the sample weight. When switch 61is closed, the voltage representing the logarithm of the sample weightis subtracted from that representing the logarithm of the ionconcentration and the resultant electrical output from subtractercircuit 68 is proportional to the logarithm of concentration divided byweight. The subtracter output voltage is coupled to antilog circuit 69which provides a voltage proportional to concentration divided byweight. The analog-to-digital converter 70 converts this voltage to adigital signal representative of concentration divided by weight. Duringthe time that switch 62 is closed, pulse generator 78 provides theprinter-controller with a pulse every two seconds which causes thedigital output of converter 70 to be transmitted to printer 76 andaccumulated every two seconds for the duration of the integrate stepwhich in this example is two minutes.

At the beginning of the reset step, di-verter valves 44 and 46 return tothe position shown in FIG. 1 and switch 62 opens so that no furtheroutputs from converter 70 are accumulated. During this step vent valve34 and switch 61 remain closed. This step provides a buffer time periodbefore the totalizing step is performed and prevents errors fromoccurring due to transient conditions.

During the tenth and final step the drain valve 35 is opened and tank 33is permitted to drain. Although it has not been illustrated in thedrawings, a source of water or other suitable liquid could be connectedto tank 33 during a portion of this step to rinse any residue therefrom.It is to be noted that the tank need not drain completely betweensuccessive samplings. In one successful operation of the disclosedapparatus, the tank drained only about 80% before being refilled. Duringthe tenth step, switch 63 closes and connects DC potential source 79 toprinter-controller 75 through capacitor 80. The effect of this capacitoris to cause an electrical pulse to be delivered to theprinter-controller to initiate the totalize function. After this initialpulse, capacitor 80' blocks further flow of current.

The overall function of the system described hereinabove is to performan integration of the concentration of ions in the stream of solutionflowing through sensing chamber 53 divided by the sample weight.Although the integration function was terminated after a two-minuteperiod in the example given, the accuracy of this method is practicallyunaffected since the concentration of the solution flowing through thesensing chamber after the elapse of two minutes is very low and its rateof change is low. If the flow of the carrier fluid-solution mixture pastthe ion sensing electrodes is substantially constant, the result of thisintegration is proportional to the percent of sodium ions in the sample.If the original sodium containing compound is known, this system couldbe calibrated to read numerical percent of that compound, e.g., Na O orNa CO as required.

The embodiment shown in FIG. 1 must be modified when the sample to betested contains solids which are not soluble in water. One possiblemodification would be to merely connect the nozzle 40 with a source ofthe proper solvent. Another embodiment which may be used for dissolvingsamples, which are not soluble in water, is shown in FIG. 4 whereincomponents similar to those in FIG. 1 are indicated by primed referencenumerals. Dissolving tank 33' is provided with a cell 83 from which pHsensing and reference electrodes extend into the interior of the tank. Abasic solution source 84 is connected to tank 33 by a pipe 85 having avalve 86 therein, and an acidic solution source 87 is connected to tank33' by a pipe 88 hav- 6 ing a valve 89 therein. The electrical outputfrom cell 83 is coupled to a pH meter and control circuit 90 whichcontrols the operation of valves 86 and 89. Circuit 90 may be of thetype disclosed in US. Pat. No. 2,726,670 entitled Flow ControlApparatus, issued to J. J. I. Staunton on Dec. 13, 1955.

The tank "33 is initially filled with the sample and a predeterminedamount of water by utilizing the apparatus of FIG. 1, then acid fromsource 87 is added until the pH of the solution is about 3. At this timecircuit 90 responds to the voltage from cell 83 and closes valve 89.After the sample and the acidic solvent are mixed for a time sufficientto dissolve the sample, the valve 86 is opened and the basic solutionfrom source 84 is added to the tank 33' until the solution isneutralized and the pH thereof is raised to about 7. Thereafter theprocess may resume at step 8 as described in conjunction with FIG. 3.

The embodiment shown in FIG. 4 may be used, for example, whendetermining the percentage of limestone (calcium carbonate) or magnesia(magnesium carbonate) in a batch. In either case HCl is added to thesample to form a solution, and after a suflicient time, the solution isneutralized with ammonium hydroxide. In practicing this invention othersolvents may be used which may or may not require the use ofneutralizing fluid. The few examples set forth herein are not to beconsidered as limiting the scope of this invention, but are exemplary ofsome of the many processes within the scope thereof.

FIG. 5 is a graph illustrating an X-Y recorder plot of the ion sensingelectrode response to a pulse of solution washed from dissolving tank 33to sensing chamber 53. Some of the solution from tank 33 mixes withwater which was in pipe 48 prior to switching valves 44 and 46. Thiscauses a gradual initial slope in curve which is beneficial in that thespecific ion electrode could not instantaneously follow an abrupt changefrom water to sample solution in sensing chamber 53. It is the areaunder curve 95 which provides a determination of the percentage of agiven type of soluble ions in the sample mixture dissolved in tank 33with an accuracy of 11%. The method of the present invention providesmore accurate results than would be obtained by placing the ion sensingelectrode directly in the dissolving tank '33, since ion sensingelectrodes are more stable in a continuously flowing stream, and sinceit is simpler to provide a substantially constant :flow through thesensing chamber than to meter a fixed weight of water or other solventto a dissolving tank as would be required if the sensing electrodes werein the dissolving tank.

In the heretofore described preferred embodiment the integration timewas two minutes, and the integration process was initiatedsimultaneously with the switching of valves 44 and 46. If the volume ofthe pipework 48, 50 and 52, cyclone 51 and sensing chamber 53 were toogreat, the initiation of the integration process would have to bedelayed since the mixture of the carrier fluid and the solvent from tank33 would not have reached sensing chamber 53 for some appreciable timeafter integration had been initiated. Initiation of the integrationperiod too soon before an electrical output is provided by the sensingchamber will introduce error in the output of the system. In thosesystems wherein a delay is experienced between the time that valves 44and 46 are switched and an output signal is provided by chamber 53, theinteg ration process should be delayed until the time that the sensingchamber provides an output. This time delay could be a predeterminedtime after valves 44 and 46 are switched or it could be determined bydetecting the output of chamber 53 and using the detected signal toinitiate integration.

Although the integration period was two minutes in the describedembodiment, this period depends upon the physical parameters of thesystem. Integration time is affected by such parameters as flow rate ofcarrier fluid,

volume of solution to be mixed with carrier fluid, volume of pipeworkand chambers between mixing point and sensing chamber, volume andphysical configuration of sensing chamber, and the like. Integrationtime must be long enough that the entire peak shape is integrated (seeFIG. but it should not be so long that baseline changes encountered atlong integration times could introduce noise into the results. Thesystem can be calibrated and the optimum integration time period can bedetermined by running known concentrations of the detected element orcompound through the system and observing that integration time whichprovides most accurate results.

Numerous modifications could be made to the described method withoutdeparting from the scope of this invention. For example, if the granularsample were manually weighed, as previously suggested, a predeterminedweight could be dissolved in chamber 33 so that the output of the systemwould indicate the concentration of the measured element or compound.Obviously, the weigh cell and the circuitry up to and includingsubtractor 66 would not be necessary to perform a method includingmanual weighing. A slight modification of this method would entail theadjustment of a potentiometer dial which could be calibrated in units ofweight. The pointer would be set to the weight of the manually weighedsample the output voltage from the potentiometer could be connected tosubtractor 68.

Although the preferred embodiment described the preparation of asolution from a solvent and a granular material, this step could bedispensed with if the element or compound under investigation werealready in an exist ing solution. For example, the apparatus of FIG. 1could be utilized to test river water, factory effluence or the like.Such solution could be directly injected into tank 33. If a knownquantity of such solution were used, the concentration of elementscontained therein could be determined. Circuitry similar to that of FIG.4 could be used if an electrical level indicator in tank 33 provided asignal indicative of the quantity of solution in tank 33. This signalcould be applied to transconductor 73 of FIG. 2. Otherwise the apparatusof FIGS. 1 and 2 could operate as previously described.

The carrier fluid need not be totally deflected through the tank 33; theprocess of this invention could be carried out by deflecting only a partof the carrier fluid. Thus valves 44 and 46 could be of the type thatcould be adjusted to cause some of the carrier fluid to flow throughtank 33, the remainder flowing through pipe and combining with themixture flowing from tank 33 in valve 46. This method of operation wouldrequire a longer integration time for a given total flow through pipe43, since a longer period of time would be required to generate peakshape of the curve of FIG. 5.

No carrier fluid need flow through the tank in which the solution isstored if the solution is injected into the stream of carrier fluid. Asshown in FIG. 6, wherein elements similar to those of FIG. 1 areindicated by primed reference numerals, a solution stored in tank 97 isinjected into a carrier stream flowing through pipes 43' and 48 byopening valve 98 and depressing plunger 99. The rate of mixing ofcarrier fluid and solution is determined by the rate at which thesolution is injected into the carrier fluid. After the system iscalibrated and the optimum integration time is determined, concentrationof elements contained in the injected solution can be accuratelydetermined. Tank 97 could be similar to dissolving tank 33 of FIG. 1,and compressed air could be applied to some inlet pipe such as pipe 49to force the solution contained in the tank to emanate therefrom and beinjected into a carrier stream.

I claim:

1. Apparatus for determining the concentration of an element in asolution comprising means for retaining a sample of said solution,

a chamber containing at least one ion sensing electrode, said electrodebeing specifically sensitive to ions of said element,

means for supplying said chamber with a stream of carrier fluid,

means for mixing said solution with said carrier fluid andsimultaneously conveying the resultant mixture to said chamber in such amanner that the concentration of said element in said mixture increasesfrom a first minimum value to a maximum value and thereafter decreasesto a second minimum value at which the rate of change of concentrationwith time is negligible, the period of time between the occurence ofsaid first and second minimum values constituting a given period oftime, the electrical output of said ion sensing electrode continuouslyindicating the concentration of a specific ion in the liquid mixturereaching said chamber during said given period of time, and

means for integrating said electrical output from said electrode forsaid given period of time.

2. Apparatus in accordance with claim 1 wherein said means for mixingincluding valve means for diverting at least a portion of said carrierfluid through said sample retaining means and for flowing said mixtureback into the path of said carrier stream whereby said mixture isconveyed to said chamber.

3. Apparatus in accordance with claim 1 wherein said means for mixingcomprises means for injecting said solution into said carrier stream toform said mixture.

4. Apparatus in accordance with claim 1 further comprising means forremoving undissolved solids from said mixture.

5. Apparatus in accordance with claim 1 further comprising means forsupplying a weighed sample of granular solids to said sample retainingmeans,

means for supplying a solvent to said sample retaining means, and,

means for combining said granular solids and said solvent to form asolution.

6. Apparatus in accordance with claim 5 wherein said means for supplyinga solvent comprises means for supplying an acidic solution to saidsample retaining means, said apparatus further comprising means forsupplying a basic solution to said sample retaining means, and meansresponsive to the pH of said solution for controlling the flow of saidacidic and basic solutions.

7. Apparatus in accordance with claim 5 wherein said means for combiningsaid sample and said solvent comprise a pipeline connected between thebottom and top of said sample retaining means and a pump in saidpipeline.

8. Apparatus for determining the concentration of an element in asolution comprising means for retaining a sample solution,

means for supplying a weighed sample including a weigh cell having aweigh hopper suspended there from for retaining a weighed sample ofgranular solids, said weigh cell providing an electrical signalindicative of the weight of said granular solids,

means for dumping the contents of said weigh hopper into said sampleretaining means,

means for supplying a solvent to said sample retaining means,

means for combining said granular solids and said solvent to form asolution,

a chamber containing at least one ion sensing electrode,

means for supplying said chamber with a stream of carrier fluid, and

means for mixing said solution with said carrier fluid so that theresultant mixture is conveyed to said chamber, the electrical output ofsaid ion sensing electrode continuously indicating the concentration ofa specific ion in the liquid mixture reaching said chamber;

9. Apparatus in accordance with claim 8 wherein said means for supplyinga weighed sample further comprises means for intercepting said samplefrom a source of granular solids and delivering said sample to saidweigh hopper.

10. Apparatus for determining the concentration of an element in asolution comprising means for retaining a sample solution,

a weigh cell having a weigh hopper suspended therefrom for retaining aweighed sample of granular solids, said weigh cell providing anelectrical signal indicative of the weight of said granular solids,

electrically controlled means for dumping the contents of said weighhopper into said sample retaining means,

means for supplying a solvent to said sample retaining means,

means for combining said solvent to form a solution,

a chamber containing at least one ion sensing electrode,

means for supplying said chamber with a stream of carrier fluid,

means for mixing said solution with said carrier fluid so that theresultant mixture is conveyed to said chamber, the electrical output ofsaid ion sensing electrode continuously indicating the concentration ofa specific ion in the liquid mixture reaching said chamber, and

electronic circuit means connected to said ion sensing electrode andsaid weigh cell output for providing an output electrical signalproportional to the concentration of said element divided by the weightof said sample.

11. Apparatus in accordance with claim 10 further comprising sample andhold circuit means for providing an elecgranular solids and said tricalsignal proportional to the weight of sample 7 dumped from said weighhopper into said sample retaining means,

non-linear means connected to said sample and hold circuit for providingan electrical signal proportional to the logarithm of the output of saidsample and hold circuit,

a subtracter circuit having one input connected to the output of saidnon-linear means,

means connecting the electrical output signal from said ion sensingelectrode to said subtracter circuit, said subtracter circuit providingan output voltage pro- 1'0 portional to said ion sensing electrodeoutput minus the output from said non-linear means, and antilog meansconnected to the output of said subtracter circuit for providing anelectrical signal proportional to the concentration of said elementdivided by the weight of said sample.

12. Apparatus in accordance with claim 11 wherein means for integratingis connected to the output of said antilog means.

13. Apparatus in accordance with claim 11 further comprising ananalog-to-digital converter connected to said antilog means, and meansto periodically totalize the output of said converter.

14. Apparatus for determining the concentration of an element in asample mixture of granular solids comprising dissolving means forretaining a sample containing solution,

means for supplying a weighed sample of granular solids to saiddissolving means,

means for supplying a solvent to said dissolving means,

means for combining said sample and said solvent to form a solution,

a chamber containing at least one ion sensing electrode,

means for supplying said chamber with a stream of carrier fluid, and

valve means for diverting said carrier fluid through said dissolvingmeans whereby said solution is mixed with said carrier fluid and theresultant mixture is conveyed to said chamber, the electrical output ofsaid ion sensing electrode continuously indicating the concentration ofa specific ion in the liquid mixture reaching said chamber.

15. Apparatus in accordance with claim 14 further comprising means forintegrating said electrical output from said electrode for a givenperiod of time.

References Cited UNITED STATES PATENTS 3,654,113 4/1972 Bochinski 204l T3,210,261 10/1965 Tyler 204-1 T 3,208,926 9/1965 Eckfeldt 2041 T JOHN H.MACK, Primary Examiner W. I. SOLOMON, Assistant Examiner US. Cl. X.R.324-29, 71 R

